Laundry care compositions with thiazolium dye

ABSTRACT

The present invention relates to thiazolium dyes, laundry care compositions comprising one or more thiazolium dyes, processes of making such dyes and laundry care compositions and methods of using same. The dyes, compositions and methods of the present invention are advantageous in providing improved hueing of fabric, including whitening of white fabric, while avoiding significant build up of bluing dyes on the fabric.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119(e) to U.S.Provisional Application Ser. No. 60/761,428 filed Jan. 23, 2006.

FIELD OF THE INVENTION

The present invention relates to thiazolium dyes, laundry carecompositions comprising one or more thiazolium dyes, processes of makingsuch dyes and laundry care compositions and methods of using same.

BACKGROUND OF THE INVENTION

Fabrics, typically lighter colored fabrics such as white fabrics, thatare worn and/or laundered typically discolor. For example, white fabricswhich are repeatedly laundered can exhibit a yellowing in colorappearance which causes the fabric to look older and worn. In an effortto overcome such fabric discoloration, certain laundry detergentproducts include a hueing or bluing dye which attaches to fabric duringthe laundry wash and/or rinse cycle. Unfortunately, such hueing orbluing dye typically tends to accumulate on the fabric, thus giving thefabric an undesirable bluish tint. As a result, a chlorine treatment isgenerally employed to reduce the aforementioned accumulation of bluingdyes. While a chlorine treatment can be effective, it is an additional,inconvenient step in the laundry process. Additionally, a chlorinetreatment is costly and harsh on fabrics—contributing to increasedfabric degradation. Accordingly, a need exists for improved laundry careproducts which can counter the undesirable discoloration of fabrics,including the yellowing of white fabrics.

SUMMARY OF THE INVENTION

The present invention relates to thiazolium dyes, laundry carecompositions comprising one or more thiazolium dyes, processes of makingsuch dyes and laundry care compositions and methods of using same. Thedyes, compositions and methods of the present invention are advantageousin providing improved hueing of fabric, including whitening of whitefabric, while avoiding significant build up of bluing dyes on thefabric.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, bar formand/or flake type washing agents and/or fabric treatment compositions.

As used herein, the term “fabric treatment composition” includes, unlessotherwise indicated, fabric softening compositions, fabric enhancingcompositions, fabric freshening compositions and combinations there of.Such compositions may be, but need not be rinse added compositions.

As used herein, the articles including “the”, “a” and “an” when used ina claim, are understood to mean one or more of what is claimed ordescribed.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

As used herein, the term polyether is defined as at least two repeatingether units that are chemically bound via the ethers' oxygen atoms. Suchpolyethers may be derived from materials including but not limited toethylene oxide, propylene oxide, butylene oxide, hexylene oxide,glycidol, epichlorohydrin, pentanerythritol, glucose or combinationsthereof.

As used herein capped polyether means a polyether that terminates in analkyl or aryl moiety, including but not limited to a moiety selectedfrom methyl, ethyl, butyl, isopropyl, tertiary butyl, amyl, benzyl,pentyl, and acetyl moieties.

As used herein “EO” stands for an ethylene oxide moiety.

As used herein “PO” stands for a propylene oxide moiety.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

Laundry Care Compositions

In one aspect, a laundry care composition that may comprise a laundrycare ingredient and a suitable thiazolium dye is disclosed. Suitablethiazolium dyes include thiazolium dyes that exhibit good tintingefficiency during a laundry wash cycle without exhibiting excessiveundesirable build up after laundering. Thus, undesirable bluing afterrepeated washings with the detergent compositions of the invention isavoided and costly and harsh chlorine treatments are unnecessary.Suitable thiazolium dyes include those thiazolium dyes that aredescribed under the heading “Suitable Thiazolium Dyes” of the presentspecification.

In one aspect, the laundry care compositions disclosed in the presentspecification can employ the thiazolium dyes disclosed in the presentspecification as detailed by Formulae V through VIII of the presentspecification.

In one aspect suitable thiazolium dyes include thiazolium dye moleculesnumbers 1-80 as detailed in Tables 1 and 2 of the present specification.

In one aspect, suitable thiazolium dyes include thiazolium dye moleculesnumbers 1, 4, 5, 7, 8, 12, 13, 15, 16, 17, 21, 24, 25, 26, 30, 31, 33,36, 38, 40, 45 and 48 as detailed in Tables 1 and 2 of the presentspecification.

In one aspect, suitable thiazolium dyes include thiazolium dye moleculesnumbers 12, 13, 15, 16, 24, 25, 26, 30, 31, 33, 36, 38, 40, 45 and 48 asdetailed in Tables 1 and 2 of the present specification.

In one aspect, the laundry care compositions disclosed in the presentspecification can employ combinations of any of the suitable thiazoliumdyes disclosed in the present specification.

In one aspect, the laundry care compositions disclosed in the presentspecification can employ a non-hueing dye in combination with thethiazolium dye. The non-hueing dye may be selected from non-hueing dyesdisclosed in U.S. Patent Application 2005/028820 A1, U.S. Pat. No.4,137,243, U.S. Pat. No. 4,601,725 and U.S. Pat. No. 4,871,371. Whilenot being bound by theory, it is believed that the combination of both athiazolium dye and a non-hueing dye allows for flexibility to colorblend to a desired hue.

In one aspect, the laundry care compositions disclosed in the presentspecification can employ a non-hueing dye, that may be non-substantivein nature, in combination with the thiazolium dye. The combination ofboth a thiazolium dye and a non-hueing dye can allow customization ofproduct color and fabric tint. In one aspect, Acid Blue 7 may beemployed as a non-hueing, non-tinting dye.

In one aspect, any of the components, including the suitable thiazoliumdyes, may be employed in the laundry care compositions in anencapsulated form. Such encapsulates may comprise one or more of suchcomponents.

In one aspect a laundry care compositions comprising a thiazolium dyeand a laundry care ingredient and having a hueing efficiency of greaterthan 10 but less than 40, from about 15 to about 35, or even from about15 to about 30 and a wash removability of from about 30% to about 85%,from about 40% to about 85%, from about 50% to about 85% are disclosed.

Suitable laundry care ingredients include, but are not limited to, thosematerials described in the present specification as useful aspects ofthe present invention, including adjunct materials as described in thepresent specification.

Liquid, Laundry Detergent Compositions

In one aspect, the laundry care compositions disclosed herein, may takethe form of liquid, laundry detergent compositions. In one aspect, suchcompositions may be a heavy duty liquid composition. Such compositionsmay comprise a sufficient amount of a surfactant to provide the desiredlevel of one or more cleaning properties, typically by weight of thetotal composition, from about 5% to about 90%, from about 5% to about70% or even from about 5% to about 40% and a sufficient of suitablethiazolium dye that is described under the heading “Suitable ThiazoliumDyes” of the present specification, to provide a tinting effect tofabric washed in a solution containing the detergent, typically byweight of the total composition, from about 0.0001% to about 0.05%, oreven from about 0.001% to about 0.01%.

The liquid detergent compositions comprise an aqueous, non-surfaceactive liquid carrier. Generally, the amount of the aqueous, non-surfaceactive liquid carrier employed in the compositions herein will beeffective to solubilize, suspend or disperse the composition components.For example, the compositions may comprise, by weight, from about 5% toabout 90%, from about 10% to about 70%, or even from about 20% to about70% of an aqueous, non-surface active liquid carrier.

The most cost effective type of aqueous, non-surface active liquidcarrier may be water. Accordingly, the aqueous, non-surface activeliquid carrier component may be generally mostly, if not completely,water. While other types of water-miscible liquids, such alkanols,diols, other polyols, ethers, amines, and the like, have beenconventionally been added to liquid detergent compositions asco-solvents or stabilizers, for purposes of the present invention, theutilization of such water-miscible liquids may be minimized to hold downcomposition cost. Accordingly, the aqueous liquid carrier component ofthe liquid detergent products herein will generally comprise waterpresent in concentrations ranging from about 5% to about 90%, or evenfrom about 20% to about 70%, by weight of the composition.

The liquid detergent compositions herein may take the form of an aqueoussolution or uniform dispersion or suspension of surfactant, thiazoliumdye, and certain optional other ingredients, some of which may normallybe in solid form, that have been combined with the normally liquidcomponents of the composition, such as the liquid alcohol ethoxylatenonionic, the aqueous liquid carrier, and any other normally liquidoptional ingredients. Such a solution, dispersion or suspension will beacceptably phase stable and will typically have a viscosity which rangesfrom about 100 to 600 cps, more preferably from about 150 to 400 cps.For purposes of this invention, viscosity is measured with a BrookfieldLVDV-II+ viscometer apparatus using a #21 spindle.

Suitable surfactants may be anionic, nonionic, cationic, zwitterionicand/or amphoteric surfactants. In one aspect, the detergent compositioncomprises anionic surfactant, nonionic surfactant, or mixtures thereof.

Suitable anionic surfactants may be any of the conventional anionicsurfactant types typically used in liquid detergent products. Suchsurfactants include the alkyl benzene sulfonic acids and their salts aswell as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C₁₀₋₁₆ alkylbenzene sulfonic acids, preferably C₁₁₋₁₄ alkyl benzene sulfonic acids.In one aspect, the alkyl group is linear. Such linear alkyl benzenesulfonates are known as “LAS”. Such surfactants and their preparationare described for example in U.S. Pat. Nos. 2,220,099 and 2,477,383.Especially preferred are the sodium and potassium linear straight chainalkylbenzene sulfonates in which the average number of carbon atoms inthe alkyl group is from about 11 to 14. Sodium C₁₁-C₁₄, e.g., C₁₂, LASis a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O)_(n)—SO₃M wherein R′ is a C8-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In a specificembodiment, R′ is C₁₀-C₁₈ alkyl, n is from about 1 to 15, and M issodium, potassium, ammonium, alkylammonium, or alkanolammonium. In morespecific embodiments, R′ is a C₁₂-C₁₆, n is from about 1 to 6 and M issodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the compositions of thisinvention and used as or in any anionic surfactant component which maybe present. Specific examples of non-alkoyxylated, e.g.,non-ethoxylated, alkyl ether sulfate surfactants are those produced bythe sulfation of higher C8-C₂₀ fatty alcohols. Conventional primaryalkyl sulfate surfactants have the general formula: ROSO₃ ⁻M⁺ wherein Ris typically a linear C₈-C₂₀ hydrocarbyl group, which may be straightchain or branched chain, and M is a water-solubilizing cation. Inspecific embodiments, R is a C₁₀-C₁₅ alkyl, and M is alkali metal, morespecifically R is C₁₂-C₁₄ and M is sodium.

Specific, nonlimiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primary,branched-chain and random alkyl sulfates (AS); c) C₁₀-C₁₈ secondary(2,3) alkyl sulfates having formulae (I) and (II):

wherein M in formulae (I) and (II) is hydrogen or a cation whichprovides charge neutrality, and all M units, whether associated with asurfactant or adjunct ingredient, can either be a hydrogen atom or acation depending upon the form isolated by the artisan or the relativepH of the system wherein the compound is used, with non-limitingexamples of preferred cations including sodium, potassium, ammonium, andmixtures thereof, and x is an integer of at least about 7, preferably atleast about 9, and y is an integer of at least 8, preferably at leastabout 9; d) C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) wherein preferably xis from 1-30; e) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably comprising1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed inU.S. Pat. Nos. 6,020,303 a 6,060,443; g) mid-chain branched alkyl alkoxysulfates as discussed in U.S. Pat. Nos. 6,008,181 and 6,020,303; h)modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO99/07656, WO 00/23549, and WO 00/23548.; i) methyl ester sulfonate(MES); and j) alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. Preferred for use in the liquid detergent productsherein are those nonionic surfactants which are normally liquid.

Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.Preferably R¹ is an alkyl group, which may be primary or secondary, thatcontains from about 9 to 15 carbon atoms, more preferably from about 10to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcoholswill also be ethoxylated materials that contain from about 2 to 12ethylene oxide moieties per molecule, more preferably from about 3 to 10ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17. More preferably, the HLBof this material will range from about 6 to 15, most preferably fromabout 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have beenmarketed under the tradename Neodol® by the Shell Chemical Company.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O. In this formula, Ris a relatively long-chain hydrocarbyl moiety which can be saturated orunsaturated, linear or branched, and can contain from 8 to 20,preferably from 10 to 16 carbon atoms, and is more preferably C₁₂-C₁₆primary alkyl. R′ is a short-chain moiety, preferably selected fromhydrogen, methyl and —CH₂OH. When x+y+z is different from 0, EO isethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxidesurfactants are illustrated by C₁₂₋₁₄ alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as Pluronic® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x 1-30, as discussed in U.S. Pat.Nos. 6,153,577, 6,020,303 and 6,093,856; f) Alkylpolysaccharides asdiscussed in U.S. Pat. No. 4,565,647 Llenado, issued Jan. 26, 1986;specifically alkylpolyglycosides as discussed in U.S. Pat. Nos.4,483,780 and 4,483,779; g) Polyhydroxy fatty acid amides as discussedin U.S. Pat. No. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, andWO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactantsas discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactantcomponent may comprise combinations of anionic and nonionic surfactantmaterials. When this is the case, the weight ratio of anionic tononionic will typically range from 10:90 to 90:10, more typically from30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and 6,022,844; and e) amino surfactants as discussedin U.S. Pat. No. 6,221,825 and WO 00/47708, specifically amidopropyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include: derivativesof secondary and tertiary amines, derivatives of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (preferably C₁₂ to C₁₈) amine oxides and sulfo and hydroxybetaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate wherethe alkyl group can be C₈ to C₁₈, preferably C₁₀ to C₁₄.

Non-limiting examples of ampholytic surfactants include: aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents contains at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one contains an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

Granular Laundry Detergent Compositions

In one aspect, the laundry care compositions disclosed herein, may takethe form of granular, laundry detergent compositions. Such compositionsmay comprise a sufficient of suitable thiazolium dye that is describedunder the heading “Suitable Thiazolium Dyes” of the presentspecification, to provide a tinting effect to fabric washed in asolution containing the detergent, typically by weight of the totalcomposition, from about 0.0001% to about 0.05%, or even from about0.001% to about 0.01%.

Granular detergent compositions of the present invention may include anynumber of conventional detergent ingredients. For example, thesurfactant system of the detergent composition may include anionic,nonionic, zwitterionic, ampholytic and cationic classes and compatiblemixtures thereof. Detergent surfactants for granular compositions aredescribed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, andin U.S. Pat. No. 3,919,678, Laughlin et al., issued Dec. 30, 1975.Cationic surfactants include those described in U.S. Pat. No. 4,222,905,Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy,issued Dec. 16, 1980.

Nonlimiting examples of surfactant systems include the conventionalC₁₁-C₁₈ alkyl benzene sulfonates (“LAS”) and primary, branched-chain andrandom C₁₀-C₂₀ alkyl sulfates (“AS”), the C₁₀-C₁₈ secondary (2,3) alkylsulfates of the formula CH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺)CH₃ and CH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺)CH₂CH₃ where x and (y+1) are integers of at leastabout 7, preferably at least about 9, and M is a water-solubilizingcation, especially sodium, unsaturated sulfates such as oleyl sulfate,the C₁₀-C₁₈ alkyl alkoxy sulfates (“AE_(x)S”; especially EO 1-7 ethoxysulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5ethoxycarboxylates), the C₁₀₋₁₈ glycerol ethers, the C₁₀-C₁₈ alkylpolyglycosides and their corresponding sulfated polyglycosides, andC₁₂-C₁₈ alpha-sulfonated fatty acid esters. If desired, the conventionalnonionic and amphoteric surfactants such as the C₁₂-C₁₈ alkylethoxylates (“AE”) including the so-called narrow peaked alkylethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especially ethoxylatesand mixed ethoxy/propoxy), C₁₂-C₁₈ betaines and sulfobetaines(“sultaines”), C₁₀-C₁₈ amine oxides, and the like, can also be includedin the surfactant system. The C₁₀-C₁₈ N-alkyl polyhydroxy fatty acidamides can also be used. See WO 9,206,154. Other sugar-derivedsurfactants include the N-alkoxy polyhydroxy fatty acid amides, such asC₁₀-C₁₈ N-(3-methoxypropyl) glucamide. The N-propyl through N-hexylC₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀-C₂₀ conventionalsoaps may also be used. If high sudsing is desired, the branched-chainC₁₀-C₁₆ soaps may be used. Mixtures of anionic and nonionic surfactantsare especially useful. Other conventional useful surfactants are listedin standard texts.

The detergent composition can, and preferably does, include a detergentbuilder. Builders are generally selected from the various water-soluble,alkali metal, ammonium or substituted ammonium phosphates,polyphosphates, phosphonates, polyphosphonates, carbonates, silicates,borates, polyhydroxy sulfonates, polyacetates, carboxylates, andpolycarboxylates. Preferred are the alkali metal, especially sodium,salts of the above. Preferred for use herein are the phosphates,carbonates, silicates, C₁₀-₁₈ fatty acids, polycarboxylates, andmixtures thereof. More preferred are sodium tripolyphosphate,tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates,sodium silicate, and mixtures thereof.

Specific examples of inorganic phosphate builders are sodium andpotassium tripolyphosphate, pyrophosphate, polymeric metaphosphatehaving a degree of polymerization of from about 6 to 21, andorthophosphates. Examples of polyphosphonate builders are the sodium andpotassium salts of ethylene diphosphonic acid, the sodium and potassiumsalts of ethane 1-hydroxy-1, 1-diphosphonic acid and the sodium andpotassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorusbuilder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030;3,422,021; 3,422,137; 3,400,176 and 3,400,148. Examples ofnonphosphorus, inorganic builders are sodium and potassium carbonate,bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicateshaving a weight ratio of SiO₂ to alkali metal oxide of from about 0.5 toabout 4.0, preferably from about 1.0 to about 2.4. Water-soluble,nonphosphorus organic builders useful herein include the various alkalimetal, ammonium and substituted ammonium polyacetates, carboxylates,polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate andpolycarboxylate builders are the sodium, potassium, lithium, ammoniumand substituted ammonium salts of ethylene diamine tetraacetic acid,nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids, and citric acid.

Polymeric polycarboxylate builders are set forth in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. Such materials include thewater-soluble salts of homo- and copolymers of aliphatic carboxylicacids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid,aconitic acid, citraconic acid and methylenemalonic acid. Some of thesematerials are useful as the water-soluble anionic polymer as hereinafterdescribed, but only if in intimate admixture with the nonsoap anionicsurfactant. Other suitable polycarboxylates for use herein are thepolyacetal carboxylates described in U.S. Pat. No. 4,144,226, issuedMar. 13, 1979 to Crutchfield et al., and U.S. Pat. No. 4,246,495, issuedMar. 27, 1979 to Crutchfield et al.

Water-soluble silicate solids represented by the formula SiO₂.M₂O, Mbeing an alkali metal, and having a SiO₂:M₂O weight ratio of from about0.5 to about 4.0, are useful salts in the detergent granules of theinvention at levels of from about 2% to about 15% on an anhydrous weightbasis. Anhydrous or hydrated particulate silicate can be utilized, aswell.

Any number of additional ingredients can also be included as componentsin the granular detergent composition. These include other detergencybuilders, bleaches, bleach activators, suds boosters or sudssuppressors, anti-tarnish and anti-corrosion agents, soil suspendingagents, soil release agents, germicides, pH adjusting agents, nonbuilderalkalinity sources, chelating agents, smectite clays, enzymes,enzyme-stabilizing agents and perfumes. See U.S. Pat. No. 3,936,537,issued Feb. 3, 1976 to Baskerville, Jr. et al.

Bleaching agents and activators are described in U.S. Pat. No.4,412,934, Chung et al., issued Nov. 1, 1983, and in U.S. Pat. No.4,483,781, Hartman, issued Nov. 20, 1984. Chelating agents are alsodescribed in U.S. Pat. No. 4,663,071, Bush et al., from Column 17, line54 through Column 18, line 68. Suds modifiers are also optionalingredients and are described in U.S. Pat. No. 3,933,672, issued Jan.20, 1976 to Bartoletta et al., and U.S. Pat. No. 4,136,045, issued Jan.23, 1979 to Gault et al. Suitable smectite clays for use herein aredescribed in U.S. Pat. No. 4,762,645, Tucker et al., issued Aug. 9,1988, Column 6, line 3 through Column 7, line 24. Suitable additionaldetergency builders for use herein are enumerated in the Baskervillepatent, Column 13, line 54 through Column 16, line 16, and in U.S. Pat.No. 4,663,071, Bush et al., issued May 5, 1987.

Rinse Added Fabric Conditioning Compositions

In one aspect, the laundry care compositions disclosed herein, may takethe form of rinse added fabric conditioning compositions. Suchcompositions may comprise a fabric softening active and a sufficientamount of suitable thiazolium dye, that is described under the heading“Suitable Thiazolium Dyes” of the present specification, to provide atinting effect to fabric treated by the composition, typically fromabout 0.00001 wt. % (0.1 ppm) to about 1 wt. % (10,000 ppm), or evenfrom about 0.0003 wt. % (3 ppm) to about 0.03 wt. % (300 ppm) based ontotal rinse added fabric conditioning composition weight. In anotherspecific embodiment, the compositions are rinse added fabricconditioning compositions. Examples of typical rinse added conditioningcomposition can be found in U.S. Provisional Patent Application Ser. No.60/687582 filed on Oct. 8, 2004.

In one embodiment of the invention, the fabric softening active(hereinafter “FSA”) is a quaternary ammonium compound suitable forsoftening fabric in a rinse step. In one embodiment, the FSA is formedfrom a reaction product of a fatty acid and an aminoalcohol obtainingmixtures of mono-, di-, and, in one embodiment, triester compounds. Inanother embodiment, the FSA comprises one or more softener quaternaryammonium compounds such, but not limited to, as a monoalkyquaternaryammonium compound, a diamido quaternary compound and a diesterquaternary ammonium compound, or a combination thereof.

In one aspect of the invention, the FSA comprises a diester quaternaryammonium (hereinafter “DQA”) compound composition. In certainembodiments of the present invention, the DQA compounds compositionsalso encompasses a description of diamido FSAs and FSAs with mixed amidoand ester linkages as well as the aforementioned diester linkages, allherein referred to as DQA.

A first type of DQA (“DQA (1)”) suitable as a FSA in the present CFSCincludes a compound comprising the formula:{R_(4−m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)} X⁻wherein each R substituent is either hydrogen, a short chain C₁-C₆,preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g., methyl (mostpreferred), ethyl, propyl, hydroxyethyl, and the like, poly (C₂-C₃alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; eachm is 2 or 3; each n is from 1 to about 4, preferably 2; each Y is—O—(O)C—, —C(O)—O—, —NR—C(O)—, or —C(O)—NR— and it is acceptable foreach Y to be the same or different; the sum of carbons in each R¹, plusone when Y is —O—(O)C— or —NR—C(O)—, is C₁₂-C₂₂, preferably C₁₄-C₂₀,with each R¹ being a hydrocarbyl, or substituted hydrocarbyl group; itis acceptable for R¹ to be unsaturated or saturated and branched orlinear and preferably it is linear; it is acceptable for each R¹ to bethe same or different and preferably these are the same; and X⁻ can beany softener-compatible anion, preferably, chloride, bromide,methylsulfate, ethylsulfate, sulfate, phosphate, and nitrate, morepreferably chloride or methyl sulfate. Preferred DQA compounds aretypically made by reacting alkanolamines such as MDEA(methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Somematerials that typically result from such reactions includeN,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride orN,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium methylsulfatewherein the acyl group is derived from animal fats, unsaturated, andpolyunsaturated, fatty acids, e.g., tallow, hardended tallow, oleicacid, and/or partially hydrogenated fatty acids, derived from vegetableoils and/or partially hydrogenated vegetable oils, such as, canola oil,safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, talloil, rice bran oil, palm oil, etc. Non-limiting examples of suitablefatty acids are listed in U.S. Pat. No. 5,759,990 at column 4, lines45-66. In one embodiment the FSA comprises other actives in addition toDQA (1) or DQA. In yet another embodiment, the FSA comprises only DQA(1) or DQA and is free or essentially free of any other quaternaryammonium compounds or other actives. In yet another embodiment, the FSAcomprises the precursor amine that is used to produce the DQA.

In another aspect of the invention, the FSA comprises a compound,identified as DTTMAC comprising the formula:[R_(4−m)—N(⁺)—R¹ _(m)]A⁻wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, preferably C₁₄-C₂₀, butno more than one being less than about C₁₂ and then the other is atleast about 16, hydrocarbyl, or substituted hydrocarbyl substituent,preferably C₁₀-C₂₀ alkyl or alkenyl (unsaturated alkyl, includingpolyunsaturated alkyl, also referred to sometimes as “alkylene”), mostpreferably C₁₂-C₁₈ alkyl or alkenyl, and branch or unbranched. In oneembodiment, the Iodine Value (IV) of the FSA is from about 1 to 70; eachR is H or a short chain C₁-C₆, preferably C₁-C₃ alkyl or hydroxyalkylgroup, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, andthe like, benzyl, or (R² O)₂₋₄H where each R² is a C₁-C₆ alkylene group;and A⁻ is a softener compatible anion, preferably, chloride, bromide,methylsulfate, ethylsulfate, sulfate, phosphate, or nitrate; morepreferably chloride or methyl sulfate. Examples of these FSAs includedialkydimethylammonium salts and dialkylenedimethylammonium salts suchas ditallowdimethylammonium and ditallowdimethylammonium methylsulfate.Examples of commercially available dialkylenedimethylammonium saltsusable in the present invention are di-hydrogenated tallow dimethylammonium chloride and ditallowdimethyl ammonium chloride available fromDegussa under the trade names Adogen® 442 and Adogen® 470 respectively.In one embodiment the FSA comprises other actives in addition to DTTMAC.In yet another embodiment, the FSA comprises only compounds of theDTTMAC and is free or essentially free of any other quaternary ammoniumcompounds or other actives.

In one embodiment, the FSA comprises an FSA described in U.S. Pat. Pub.No. 2004/0204337 A1, published Oct. 14, 2004 to Corona et al., fromparagraphs 30-79.

In another embodiment, the FSA is one described in U.S. Pat. Pub. No.2004/0229769 A1, published Nov. 18, 2005, to Smith et al., on paragraphs26-31; or U.S. Pat. No. 6,494,920, at column 1, line 51 et seq.detailing an “esterquat” or a quaternized fatty acid triethanolamineester salt.

In one embodiment, the FSA is chosen from at least one of the following:ditallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methylsulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, orcombinations thereof.

In one embodiment, the FSA may also include amide containing compoundcompositions. Examples of diamide comprising compounds may include butnot limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammoniummethyl sulfate (available from Degussa under the trade names Varisoft110 and Varisoft 222). An example of an amide-ester containing compoundisN-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.

Another specific embodiment of the invention provides for a rinse addedfabric care composition further comprising a cationic starch. Cationicstarches are disclosed in US 2004/0204337 A1. In one embodiment, thefabric care composition comprises from about 0.1% to about 7% ofcationic starch by weight of the laundry care composition. In oneembodiment, the cationic starch is HCP401 from National Starch.

Suitable Thiazolium Dyes

Suitable thiazolium dyes include azo dyes that may have Formula (I)below:

-   -   wherein:        -   R₃ and R₄ may be identical or different and, independently            of one another, are hydrogen, a saturated or unsaturated            (C₁-C₂₂)-alkyl group, a (C₁-C₂₂)-alkyl group substituted by            a halogen atom, a hydroxy-(C₂-C₂₂)-alkyl group optionally            interrupted by oxygen, a polyether group derived from            ethylene oxide, propylene oxide or butylene oxide, an            amino-(C₁-C₂₂)-alkyl group, a substituted or unsubstituted            phenyl group or a benzyl group, a (C₁-C₂₂)-alkyl group            terminated in sulfonate, sulfate, or carboxylate, or the            radical groups R₃ and R₄, together with the remaining            molecule, can form a heterocyclic or carbocyclic, saturated            or unsaturated, substituted or unsubstituted ring system            optionally substituted by halogen, sulfate, sulfonate,            phosphate, nitrate, and carboxylate;        -   X may be a radical group of the phenol series or a            heterocyclic radical group or aniline series or m-toluidine            series that may have Formula II below;

-   -   -   -   wherein:                -   R₅ and R₆ may be identical or different and,                    independently of one another, are a straight or                    branched saturated or unsaturated (C₁-C₂₂)-alkyl                    group, a (C₁-C₂₂)-alkyl ether group, a                    hydroxy-(C₂-C₂₂)-alkyl group optionally interrupted                    by oxygen, a polyether group derived from ethylene                    oxide, propylene oxide, butylene oxide, glycidyl or                    combinations thereof, an amino-(C₁-C₂₂)-alkyl group,                    a substituted or unsubstituted phenyl group or a                    benzyl group, a linear or branched (C₁-C₂₂)-alkyl                    group terminated in a linear or branched                    (C₁-C₂₂)-alkyl, hydroxyl, acetate, sulfonate,                    sulfate, or carboxylate, group or R₅ and R₆ or R₅                    and R₇ or R₆ and R₇, together with the nitrogen                    atom, form a 5-membered to 6-membered ring system,                    which may comprise a further heteroatom; or R₅ and                    R₆ or R₅ and R₇ or R₆ and R₇, form with a carbon                    atom of the benzene ring an optionally                    oxygen-containing or nitrogen containing five or                    six-membered heterocycle which may be substituted                    with one or more (C₁-C₂₂)-alkyl group;                -   R₇ may be identical or different and, independently                    of one another, are hydrogen, a halogen atom, a                    saturated or unsaturated (C₁-C₂₂)-alkyl group, a                    (C₁-C₂₂)-alkyl ether group, a hydroxyl group, a                    hydroxy-(C₁-C₂₂)-alkyl group, a (C₁-C₂₂)-alkoxy                    group, a cyano group, a nitro group, an amino group,                    a (C₁-C₂₂)-alkylamino group, a (C₁-C₂₂)-dialkylamino                    group, a carboxylic acid group, a                    C(O)O—(C₁-C₂₂)-alkyl group, a substituted or                    unsubstituted C(O)O— phenyl group;

        -   Q⁻ may be an anion that balances the overall charge of the            compound of Formula I, and the index q may be either 0 or 1.            Suitable anions include chloro, bromo, methosulfate,            tetrafluoroborate, and acetate anions.

        -   R¹ may be a (C₁-C₂₂)-alkyl, an alkyl aromatic or an alkyl            sulfonate radical having Formula (III) below;

-   -   -   -   wherein                -   R₂ is hydrogen, methyl, ethyl, propyl, acetate or a                    hydroxyl group; m and p are integers from 0 to                    (n−1), n is an integer from 1 to 6 and m+p=(n−1);                    with the proviso that the heterocycle of the                    Formula (I) comprises at least two and at most three                    heteroatoms, where the heterocycle has at most one                    sulfur atom;

In one aspect, a suitable thiazolium dye may have Formula IV below:

wherein R₈ and R₉ may be identical or different and, independently ofone another, may be a saturated or unsaturated (C₁-C₂₂)-alkyl group, a(C₁-C₂₂)-alkyl group, a hydroxy-(C₂-C₂₂)-alkyl group optionallyinterrupted by oxygen, a polyether group derived from ethylene oxide,propylene oxide or butylene oxide, an amino-(C₁-C₂₂)-alkyl group, asubstituted or unsubstituted phenyl group or a benzyl group, a(C₁-C₂₂)-alkyl group terminated in sulfonate, sulfate, or carboxylate,or R₈ and R₉, together with the nitrogen atom, may form a 5-membered to6-membered ring system, which may comprise a further heteroatom; or R₈or R₉ may form, with a carbon atom of the benzene ring, an optionallyoxygen-containing or nitrogen containing five or six-memberedheterocycle which may be substituted with one or more (C₁-C₂₂)-alkylgroups, and mixtures thereof, and R₁₀ is hydrogen or methyl. For FormulaIV, Q⁻ is as described for Formula I above.

In one aspect, suitable thiazolium dyes may have Formula (V);

-   -   wherein:        -   a.) R₁ may be selected from a branched or unbranched            (C₁-C₂₂)-alkyl moiety, an aromatic alkyl moiety, a            polyalkylene oxide moiety, or a moiety having Formula (VI)            below;

-   -   -   -   wherein                -   (i) R₂ may be selected from hydrogen, methyl, ethyl,                    propyl, acetate or a hydroxyl moiety; m and p may                    be, independently, integers from 0 to (n−1), with                    the proviso that n is an integer from 1 to 6 and m+p                    =(n−1)                -   (ii) Y may be selected from a hydroxyl, sulfonate,                    sulfate, carboxylate or acetate moiety;

        -   b.) R₃ and R₄:            -   i.) may be independently selected from hydrogen; a                saturated or unsaturated (C₁-C₂₂)-alkyl moiety; a                hydroxy-(C₂-C₂₂)-alkyl moiety; a hydroxy-(C₂-C₂₂)-alkyl                moiety comprising, in addition to the hydroxyl oxygen,                an oxygen atom; a polyether moiety; an                amino-(C₁-C₂₂)-alkyl moiety; a substituted or                unsubstituted phenyl moiety; a substituted or                unsubstituted benzyl moiety; a (C₁-C₂₂)-alkyl moiety                terminated in sulfonate, sulfate, acetate, or                carboxylate; or            -   ii.) when taken together may form a saturated or                unsaturated heterocyclic or carbocyclic moiety; or            -   iii.) when taken together may form a saturated or                unsaturated heterocyclic or carbocyclic moiety                substituted by, sulfate, sulfonate, phosphate, nitrate,                and carboxylate;

        -   c.) X may be moiety having Formula VII below;

-   -   -   -   wherein:            -   i.) R₅ and R₆:                -   (a) may be independently selected from hydrogen; a                    saturated or unsaturated (C₁-C₂₂)-alkyl moiety; a                    hydroxy-(C₂-C₂₂)-alkyl moiety; a                    hydroxy-(C₂-C₂₂)-alkyl moiety comprising, in                    addition to the hydroxyl oxygen, an oxygen atom; a                    capped or uncapped polyether moiety; an                    amino-(C₁-C₂₂)-alkyl moiety; a substituted or                    unsubstituted phenyl moiety; a substituted or                    unsubstituted benzyl moiety; a (C₁-C₂₂)-alkyl moiety                    comprising a terminating C₁-C₄ alkyl ether,                    sulfonate, sulfate, acetate or carboxylate moiety; a                    thiazole moiety or                -   (b) when taken together may form a saturated or                    unsaturated heterocyclic moiety; or                -   (c) when taken together form a saturated or                    unsaturated heterocyclic moiety substituted by one                    or more, alkoxylate, sulfate, sulfonate, phosphate,                    nitrate, and/or carboxylate moieties;                -   (d) when taken together with R₇, R₈, or R₇ and R₈                    form one or more saturated or unsaturated                    heterocyclic moieties, optionally substituted by one                    or more alkoxylate, sulfate, sulfonate, phosphate,                    nitrate, and/or carboxylate moieties; or                -   (e) when taken together form a thiazole moiety;            -   ii.) R₇ and R₈ may be independently selected from                hydrogen or a saturated or unsaturated alkyl moiety;

        -   d.) Q⁻ may be an anion that balances the overall charge of            the compound of Formula I, and the index q is 0 or 1.            Suitable anions include chloro, bromo, methosulfate,            tetrafluoroborate, and acetate anions.

In one aspect, for Formula V:

a.) R₁ may be a methyl moiety;

b.) R₃ and R₄ may be hydrogen; and

c.) X may have Formula VIII below:

-   -   wherein        -   (i) R₅ and R₆ may be as defined for Formula VII above;        -   (ii) R₇ may be hydrogen or a methyl moiety; and        -   (iii) R₈ may be hydrogen.

In one aspect, for Formula VII R₅ and R₆ each comprise, independently,from 1 to 20 alkylene oxide units and, independently, a moiety selectedfrom the group consisting of: styrene oxide, glycidyl methyl ether,isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl glycidylether, 2-ethylhexylgycidyl ether, or glycidylhexadecyl ether.

In one aspect, suitable thiazolium dyes are set forth in Table I belowand are defined as Table 1 Thiazolium Dyes. The chemical names, asdetermined by ChemFinder software Level:Pro; Version 9.0 available fromCambridgeSoft, Cambridge, Mass., U.S.A., for such dyes are respectivelyprovided in Table 2 below. Such dyes are associated, as needed tobalance the molecule's charge, with an anion Q⁻. Such anion is not shownin the structures below but for the purposes of the presentspecification is assumed to be present as required. Such anion is asdescribed above for Formula (I).

TABLE 1 No. Structure 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

TABLE 2 No. Name 1(E)-2-((4-(benzyl(methyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 2(E)-2-((4-(dimethylamino)phenyl)diazenyl)-3-methylthiazol-3-ium 3(E)-2-((4-(bis(2-hydroxyethyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium4(E)-2-((4-(bis(2-(2-(2-hydroxyethoxy)ethoxy)ethyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 5(E)-2-((4-(bis(2-(2-hydroxyethoxy)ethyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 6(E)-2-((4-(bis(14-hydroxy-5,8,11-trimethyl-3,6,9,12-tetraoxapentadecyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 7(E)-2-((4-(bis(2-(2-(2-(2-hydroxypropoxy)propoxy)propoxy)ethyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 8 (E)-2-((4-(bis(2-(2-(2-hydroxypropoxy)propoxy)ethyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium9 (E)-2-((4-(bis(35-hydroxy-5,8,11,14,17,20,23-heptamethyl-3,6,9,12,15,18,21,24,27,30,33-undecaoxapentatriacontyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 10(E)-2-((4-(bis(3-(2,3-dihydroxypropoxy)-2-hydroxypropyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 11(E)-2-((4-(bis(2,3-dihydroxypropyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 12(E)-2-((4-((2-hydroxy-3-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)propyl)(2-hydroxy-3-(2-(2-hydroxyethoxy)ethoxy)propyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 13(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 14 (E)-2-((4-(bis(35-hydroxy-17,20,23,26,29,32-hexamethyl-3,6,9,12,15,18,21,24,27,30,33-undecaoxahexatriacontyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 15(E)-2-((4-(bis(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 16(E)-2-((4-((2-(2-(2-acetoxyethoxy)ethoxy)ethyl)(2-(2-acetoxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 17 (E)-2-((4-(benzyl(2,3-dihydroxypropyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 18(E)-2-(2-((4-(bis(35-hydroxy-17,20,23,26,29,32-hexamethyl-3,6,9,12,15,18,21,24,27,30,33-undecaoxahexatriacontyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium-3-yl)acetate 19(E)-2-((4-(benzyl(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 20(E)-2-((4-((2-tert-butoxy-15-hydroxy-6,9,12-trimethyl-4,7,10,13-tetraoxahexadecyl)(2-(tert-butoxymethyl)-17-hydroxy-5,8,11,14-tetramethyl-3,6,9,12,15-pentaoxaoctadecyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 21 (E)-2-((4-(benzyl(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 22(E)-2-((4-(bis(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)-5-methoxy-3-methylbenzo[d]thiazol-3-ium 23(E)-2-(2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium-3-yl)acetate 24(E)-2-((4-(ethyl(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 25(E)-2-((4-(benzyl(1,17-dihydroxy-3,6,9,12,15-pentaoxaoctadecan-18-yl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 26(E)-2-((4-((2-(2-(2-(2,3-dihydroxypropoxy)ethoxy)ethoxy)ethyl)(2-(2-(2,3-dihydroxypropoxy)ethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 27(E)-2-(2-((4-(bis(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)-6-methoxybenzo[d]thiazol-3-ium-3-yl)acetate 28(E)-2-((4-((3-tert-butoxy-2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)propyl)(3-tert-butoxy-2-(2-(2-hydroxyethoxy)ethoxy)propyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 29(E)-2-((4-((3-butoxy-2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)propyl)(3-butoxy-2-(2-(2-hydroxyethoxy)ethoxy)propyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 30(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)-3-isopropoxypropyl)(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)-3-isopropoxypropyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 31(E)-2-((4-(benzyl(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium32(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)-3-(tridecyloxy)propyl)(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)-3-(tridecyloxy)propyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 33(E)-3-ethyl-2-((4-(ethyl(23-hydroxy-3,6,9,12,15,18,21-heptaoxatricosyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium 34(E)-2-((4-(bis(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-ethylthiazol-3-ium 35(E)-2-((1-(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)-1,2,3,4-tetrahydroquinolin-6-yl)diazenyl)-3-methylthiazol-3-ium 36(E)-2-((4-((2-(2-hydroxypropoxy)ethyl)(2-(2-(2-hydroxypropoxy)propoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 37(E)-2-((4-(bis(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-ethylthiazol-3-ium 38(E)-2-((4-(ethyl(23-hydroxy-3,6,9,12,15,18,21-heptaoxatricosyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 39(E)-2-((4-(benzyl(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)-3-ethylthiazol-3-ium 40(E)-3-ethyl-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium 41(E)-3-(2-((4-(benzyl(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium-3-yl)propane-1-sulfonate 42(E)-4-(2-((4-(benzyl(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium-3-yl)butane-1-sulfonate 43(E)-2-((4-(bis(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-ethylthiazol-3-ium 44(E)-3-benzyl-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)phenyl)diazenyl)thiazol-3-ium 45(E)-3-ethyl-2-((4-((2-(2-hydroxypropoxy)ethyl)(2-(2-(2-hydroxypropoxy)propoxy)ethyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium 46(E)-3-benzyl-2-((1-(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)-1,2,3,4-tetrahydroquinolin-6-yl)diazenyl)thiazol-3-ium 47(E)-3-benzyl-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium 48(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)propyl)(2-(2-hydroxyethoxy)propyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 49 (E)-2-((4-(benzyl(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium50 (E)-2-((4-(bis(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2,6-dimethylphenyl)diazenyl)-3-methylthiazol-3-ium 51(E)-2-((4-((4-(17-hydroxy-3,6,9,12,15-pentaoxaheptadecyloxy)-3-methoxybenzyl)(methyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 52(E)-2-((1-(1-hydroxy-2,5,8,11,14,17,20,23,26-nonaoxaoctacosan-28-yl)-1,2,3,4-tetrahydroquinolin-6-yl)diazenyl)-3-methylthiazol-3-ium 53(E)-4-(2-((4-(dimethylamino)phenyl)diazenyl)thiazol-3-ium-3-yl)butane-1-sulfonate 54(E)-4-(2-((4-(dimethylamino)phenyl)diazenyl)-5-methylthiazol-3-ium-3-yl)butane-1-sulfonate 55(E)-2-((4-((2-hydroxyethyl)(methyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 56(E)-2-(methyl(4-((3-methylthiazol-3-ium-2-yl)diazenyl)phenyl)amino)ethylsulfate 57(E)-2-((4-(butyl(2-(2-hydroxyethoxy)ethyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 58 (E)-2-((4-(bis(2-(2-(2-hydroxypropoxy)propoxy)ethyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 59 (E)-2-((4-((2-hydroxyethyl)(isopropyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 60(E)-2-((4-((14-hydroxy-3,6,9,12-tetraoxatetradecyl)(1-hydroxy-3,6,9,13-tetraoxapentadecan-15-yl)amino)-2-methylphenyl)diazenyl)-6-methoxy-3-methylbenzo[d]thiazol-3-ium 61(E)-2-((4-(benzyl(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 62(E)-2-((4-(benzyl(3-(3-(3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy)-2-hydroxypropoxy)-2-hydroxypropyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium 63(E)-3-(2-((4-(bis(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium-3-yl)propane-1-sulfonate 64(E)-2-((4-(bis(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2,5-dimethylphenyl)diazenyl)-6-methoxy-3-methylbenzo[d]thiazol-3-ium 65(E)-3-ethyl-2-((4-(ethyl(14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium 66(E)-3-ethyl-2-((1-(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)-1,2,3,4-tetrahydroquinolin-6-yl)diazenyl)thiazol-3-ium 67(E)-3-ethyl-2-((1-(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)-1,2,3,4-tetrahydroquinolin-6-yl)diazenyl)thiazol-3-ium 68(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3,5-dimethylthiazol-3-ium 69 (E)-3-ethyl-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-5-methylthiazol-3-ium 70 (E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3,5-dimethylthiazol-3-ium 71 (E)-3-ethyl-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-5-methylthiazol-3-ium 72 (E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3,5-dimethylthiazol-3-ium 732-((E)-(4-((14-hydroxy-3,6,9,12-tetraoxatetradecyl)(17-hydroxy-3-(4-((E)-thiazol-2-yldiazenyl)phenyl)-6,9,12,15-tetraoxa-3-azaheptadecyl)amino)phenyl)diazenyl)-3-methylthiazol-3-ium 74(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-methyl-5-nitrothiazol-3-ium 75(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-methyl-5-nitrothiazol-3-ium 76(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium-4-carboxylate 77(E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3,5-dimethylthiazol-3-ium-4-carboxylate 78(E)-2-((4-(benzyl(2-(tert-butoxymethyl)-17-hydroxy-3,6,9,12,15-pentaoxaheptadecyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium79 (E)-2-((4-((2-(tert-butoxymethyl)-14-hydroxy-3,6,9,12-tetraoxatetradecyl)(ethyl)amino)-2-hydroxyphenyl)diazenyl)-3-methylthiazol-3-ium 80(E)-2-((4-((13-(sec-butoxymethyl)-1-hydroxy-3,6,9,12-tetraoxapentadecan-15-yl)(2-(sec-butoxymethyl)-14-hydroxy-3,6,9,12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium

In one aspect, suitable thiazolium dyes include thiazolium dye moleculesnumbers 1, 4, 5, 7, 8, 12, 13, 15, 16, 17, 21, 24, 25, 26, 30, 31, 33,36, 38, 40, 45 and 48 as detailed in Tables 1 and 2 of the presentspecification.

In one aspect, suitable thiazolium dyes include thiazolium dye moleculesnumbers 12, 13, 15, 16, 24, 25, 26, 30, 31, 33, 36, 38, 40, 45 and 48 asdetailed in Tables 1 and 2 of the present specification.

The suitable thiazolium dyes disclosed herein may be made by proceduresknown in the art and/or in accordance with the examples of the presentspecification.

Adjunct Materials

While not essential for the purposes of the present invention, thenon-limiting list of adjuncts illustrated hereinafter are suitable foruse in the laundry care compositions and may be desirably incorporatedin certain embodiments of the invention, for example to assist orenhance performance, for treatment of the substrate to be cleaned, or tomodify the aesthetics of the composition as is the case with perfumes,colorants, dyes or the like. It is understood that such adjuncts are inaddition to the components that were previously listed for anyparticular embodiment. The total amount of such adjuncts may range fromabout 0.1% to about 50%, or even from about 1% to about 30%, by weightof the laundry care composition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable adjunct materials include, but are not limited to, polymers,for example cationic polymers, surfactants, builders, chelating agents,dye transfer inhibiting agents, dispersants, enzymes, and enzymestabilizers, catalytic materials, bleach activators, polymericdispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfume and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. In addition tothe disclosure below, suitable examples of such other adjuncts andlevels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and6,326,348 B1 that are incorporated by reference.

As stated, the adjunct ingredients are not essential to Applicants'cleaning and laundry care compositions. Thus, certain embodiments ofApplicants' compositions do not contain one or more of the followingadjuncts materials: bleach activators, surfactants, builders, chelatingagents, dye transfer inhibiting agents, dispersants, enzymes, and enzymestabilizers, catalytic metal complexes, polymeric dispersing agents,clay and soil removal/anti-redeposition agents, brighteners, sudssuppressors, dyes, additional perfumes and perfume delivery systems,structure elasticizing agents, fabric softeners, carriers, hydrotropes,processing aids and/or pigments. However, when one or more adjuncts arepresent, such one or more adjuncts may be present as detailed below:

Surfactants—The compositions according to the present invention cancomprise a surfactant or surfactant system wherein the surfactant can beselected from nonionic and/or anionic and/or cationic surfactants and/orampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.The surfactant is typically present at a level of from about 0.1%, fromabout 1%, or even from about 5% by weight of the cleaning compositionsto about 99.9%, to about 80%, to about 35%, or even to about 30% byweight of the cleaning compositions.

Builders—The compositions of the present invention can comprise one ormore detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder, or fromabout 5% or 10% to about 80%, 50%, or even 30% by weight, of saidbuilder. Builders include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates, alkali metalsilicates, alkaline earth and alkali metal carbonates, aluminosilicatebuilders polycarboxylate compounds. ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, andcarboxymethyl-oxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

Chelating Agents—The compositions herein may also optionally contain oneor more copper, iron and/or manganese chelating agents. If utilized,chelating agents will generally comprise from about 0.1% by weight ofthe compositions herein to about 15%, or even from about 3.0% to about15% by weight of the compositions herein.

Dye Transfer Inhibiting Agents—The compositions of the present inventionmay also include one or more dye transfer inhibiting agents. Suitablepolymeric dye transfer inhibiting agents include, but are not limitedto, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in the compositions herein, the dye transfer inhibiting agentsare present at levels from about 0.0001%, from about 0.01%, from about0.05% by weight of the cleaning compositions to about 10%, about 2%, oreven about 1% by weight of the cleaning compositions.

Dispersants—The compositions of the present invention can also containdispersants. Suitable water-soluble organic materials are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acid maycomprise at least two carboxyl radicals separated from each other by notmore than two carbon atoms.

Enzymes—The compositions can comprise one or more detergent enzymeswhich provide cleaning performance and/or fabric care benefits. Examplesof suitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, keratanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase,chondroitinase, laccase, and amylases, or mixtures thereof. A typicalcombination is a cocktail of conventional applicable enzymes likeprotease, lipase, cutinase and/or cellulase in conjunction with amylase.

Enzyme Stabilizers—Enzymes for use in compositions, for example,detergents can be stabilized by various techniques. The enzymes employedherein can be stabilized by the presence of water-soluble sources ofcalcium and/or magnesium ions in the finished compositions that providesuch ions to the enzymes.

Catalytic Metal Complexes—Applicants' compositions may include catalyticmetal complexes. One type of metal-containing bleach catalyst is acatalyst system comprising a transition metal cation of defined bleachcatalytic activity, such as copper, iron, titanium, ruthenium, tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobaltcatalysts are readily prepared by known procedures, such as taught forexample in U.S. Pat. Nos. 5,597,936, and 5,595,967.

Compositions herein may also suitably include a transition metal complexof a macropolycyclic rigid ligand—abbreviated as “MRL”. As a practicalmatter, and not by way of limitation, the compositions and cleaningprocesses herein can be adjusted to provide on the order of at least onepart per hundred million of the benefit agent MRL species in the aqueouswashing medium, and may provide from about 0.005 ppm to about 25 ppm,from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about5 ppm, of the MRL in the wash liquor.

Preferred transition-metals in the instant transition-metal bleachcatalyst include manganese, iron and chromium. Preferred MRL's hereinare a special type of ultra-rigid ligand that is cross-bridged such as5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.

Suitable transition metal MRLs are readily prepared by known procedures,such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.

Processes of Making Laundry Care Compositions

The laundry care compositions of the present invention can be formulatedinto any suitable form and prepared by any process chosen by theformulator, non-limiting examples of which are described in U.S. Pat.Nos. 5,879,584; 5,691,297; 5,574,005; 5,569,645; 5,565,422; 5,516,448;5,489,392; and 5,486,303.

In one aspect, the liquid detergent compositions disclosed herein may beprepared by combining the components thereof in any convenient order andby mixing, e.g., agitating, the resulting component combination to forma phase stable liquid detergent composition. In one aspect, a liquidmatrix is formed containing at least a major proportion, or evensubstantially all, of the liquid components, e.g., nonionic surfactant,the non-surface active liquid carriers and other optional liquidcomponents, with the liquid components being thoroughly admixed byimparting shear agitation to this liquid combination. For example, rapidstirring with a mechanical stirrer may usefully be employed. While shearagitation is maintained, substantially all of any anionic surfactant andthe solid ingredients can be added. Agitation of the mixture iscontinued, and if necessary, can be increased at this point to form asolution or a uniform dispersion of insoluble solid phase particulateswithin the liquid phase. After some or all of the solid-form materialshave been added to this agitated mixture, particles of any enzymematerial to be included, e.g., enzyme prills, are incorporated. As avariation of the composition preparation procedure described above, oneor more of the solid components may be added to the agitated mixture asa solution or slurry of particles premixed with a minor portion of oneor more of the liquid components. After addition of all of thecomposition components, agitation of the mixture is continued for aperiod of time sufficient to form compositions having the requisiteviscosity and phase stability characteristics. Frequently this willinvolve agitation for a period of from about 30 to 60 minutes.

In another aspect of producing liquid detergents, the thiazolium dye isfirst combined with one or more liquid components to form a thiazoliumdye premix, and this thiazolium dye premix is added to a compositionformulation containing a substantial portion, for example more than 50%by weight, more than 70% by weight, or even more than 90% by weight, ofthe balance of components of the laundry detergent composition. Forexample, in the methodology described above, both the thiazolium dyepremix and the enzyme component are added at a final stage of componentadditions. In another aspect, the thiazolium dye is encapsulated priorto addition to the detergent composition, the encapsulated dye issuspended in a structured liquid, and the suspension is added to acomposition formulation containing a substantial portion of the balanceof components of the laundry detergent composition.

Various techniques for forming detergent compositions in such solidforms are well known in the art and may be used herein. In one aspect,when the laundry care composition is in the form of a granular particle,the thiazolium dye is provided in particulate form, optionally includingadditional but not all components of the laundry detergent composition.The thiazolium dye particulate is combined with one or more additionalparticulates containing a balance of components of the laundry detergentcomposition. Further, the thiazolium dye, optionally includingadditional but not all components of the laundry detergent compositionmay be provided in an encapsulated form, and the thiazolium dyeencapsulate is combined with particulates containing a substantialbalance of components of the laundry detergent composition.

Methods of Using Laundry Care Compositions

The laundry care compositions disclosed in the present specification maybe used to clean or treat a fabric. Typically at least a portion of thefabric is contacted with an embodiment of the aforementioned laundrycare compositions, in neat form or diluted in a liquor, for example, awash liquor and then the fabric may be optionally washed and/or rinsed.In one aspect, a fabric is optionally washed and/or rinsed, contactedwith a an embodiment of the aforementioned laundry care compositions andthen optionally washed and/or rinsed. For purposes of the presentinvention, washing includes but is not limited to, scrubbing, andmechanical agitation. The fabric may comprise most any fabric capable ofbeing laundered or treated.

The laundry care compositions disclosed in the present specification canbe used to form aqueous washing solutions for use in the laundering offabrics. Generally, an effective amount of such compositions is added towater, preferably in a conventional fabric laundering automatic washingmachine, to form such aqueous laundering solutions. The aqueous washingsolution so formed is then contacted, preferably under agitation, withthe fabrics to be laundered therewith. An effective amount of thelaundry care composition, such as the liquid detergent compositionsdisclosed in the present specification, may be added to water to formaqueous laundering solutions that may comprise from about 500 to about7,000 ppm or even from about 1,000 to about 3,000 pm of laundry carecomposition.

In one aspect, one or more of the thiazolium dyes disclosed in thepresent specification may be provided, for example via a laundry carecomposition, such that during the wash cycle and or rinse cycle theconcentration of such one or more dyes may be from about 0.5 parts perbillion (ppb) to about 5 part per million (ppm), from about 1 ppb toabout 600 ppb, from about 5 ppb to about 300 ppb, or even from about 10ppb to about 100 ppb of thiazolium dye. In one aspect suchconcentrations may be achieved during the washing cycle, and/or rinsecycle, of a 17 gallon automatic laundry washing machine.

In one aspect, the laundry care compositions may be employed as alaundry additive, a pre-treatment composition and/or a post-treatmentcomposition.

TEST METHODS

I. Method For Determining of Hueing Efficiency For Detergents

-   -   a.) Two 25 cm×25 cm fabric swatches of 16 oz white cotton        interlock knit fabric (270 g/square meter, brightened with        Uvitex BNB fluorescent whitening agent, from Test Fabrics. P.O.        Box 26, Weston, Pa., 18643), are obtained.    -   b.) Prepare two one liter aliquots of tap water containing 1.55        g of AATCC standard heavy duty liquid (HDL) test detergent as        set forth in Table 3.    -   c.) Add a sufficient amount the dye to be tested to one of the        aliquots from Step b.) above to produce an aqueous solution        absorbance of 1 AU.    -   d.) Wash one swatch from a.) above in one of the aliquots of        water containing 1.55 g of AATCC standard heavy duty liquid        (HDL) test detergent and wash the other swatch in the other        aliquot. Such washing step should be conducted for 30 minutes at        room temperature with agitation. After such washing step        separately rinse the swatches and dry the swatches.    -   e.) After rinsing and drying each swatch, the hueing efficiency,        DE*_(eff), of the dye is assessed by determining the L*, a*, and        b* value measurements of each swatch using a Hunter LabScan XE        reflectance spectrophotometer with D65 illumination, 10°        observer and UV filter excluded. The hueing efficiency of the        dye is then calculated using the following equation:        DE* _(eff)=((L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*        _(s))²)^(1/2)    -    wherein the subscripts c and s respectively refer to the L*,        a*, and b* values measured for the control, i.e., the fabric        sample washed in detergent with no dye, and the fabric sample        washed in detergent containing the dye to be screened.        II. Method For Determining Wash Removability    -   a.) Prepare two separate 150 ml aliquots of HDL detergent        solution set forth in Table 1, according to AATCC Test Method        61-2003, Test 2A and containing 1.55 g/liter of the AATCC HDL        formula in distilled water.    -   b.) A 15 cm×5 cm sample of each fabric swatch from the Method        for Determining of Hueing Efficiency For Detergents described        above is washed in a Launderometer for 45 minutes at 49° C. in        150 ml of a the HDL detergent solution prepared according to        Step II. a.) above.    -   c.) The samples are rinsed with separate aliquots of rinse water        and air dried in the dark, the amount of residual coloration is        assessed by measuring the DE*_(res), of the dye is assessed by        determining the L*, a*, and b* value measurements of each swatch        using a Hunter LabScan XE reflectance spectrophotometer with D65        illumination, 10° observer and UV filter excluded. The hueing        efficiency of the dye is then calculated using the following        equation:        DE* _(res)=((L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*        _(s))²)^(1/2)    -    wherein the subscripts c and s respectively refer to the L*,        a*, and b* values measured for the control, i.e., the fabric        sample initially washed in detergent with no dye, and the fabric        sample initially washed in detergent containing the dye to be        screened. The wash removal value for the dye is then calculated        according to the formula: % removal=100×(1−DE*_(res)/DE*_(eff)).

TABLE 3 Ingredient weight percent C11.8 linear alkylbenzene sulfonicacid 12.00  Neodol 23-9 8.00 citric acid 1.20 C12-14 fatty acid 4.00sodium hydroxide¹ 2.65 ethanolamine 0.13 borax 1.00 DTPA² 0.301,2-propanediol 8.00 brightener 15 0.04 water balance ¹formula pHadjusted to 8.5 ²diethylenetriaminepentaacetic acid, pentasodium salt

EXAMPLES

The following examples illustrate the compositions of the presentinvention but are not necessarily meant to limit or otherwise define thescope of the invention herein.

Example 1

The following liquid formulas are within the scope of the presentinvention.

1a 1b 1c 1d 1e 1f⁵ Ingredient wt % wt % wt % wt % wt % wt % sodium alkylether sulfate 14.4%  14.4%  9.2% 5.4% linear alkylbenzene 4.4% 4.4%12.2%  5.7% 1.3% 22.0%  sulfonic acid alkyl ethoxylate 2.2% 2.2% 8.8%8.1% 3.4% 18.0%  amine oxide 0.7% 0.7% 1.5% citric acid 2.0% 2.0% 3.4%1.9% 1.0% 1.6% fatty acid 3.0% 3.0% 8.3% 16.0%  protease 1.0% 1.0% 0.7%1.0% 2.5% amylase 0.2% 0.2% 0.2% 0.3% lipase 0.2% borax 1.5% 1.5% 2.4%2.9% calcium and sodium 0.2% 0.2% formate formic acid 1.1% amineethoxylate polymers 1.8% 1.8% 2.1% 3.2% sodium polyacrylate 0.2% sodiumpolyacrylate 0.6% copolymer DTPA¹ 0.1% 0.1% 0.9% DTPMP² 0.3% EDTA³ 0.1%fluorescent whitening 0.15%  0.15%  0.2% 0.12%  0.12%  0.2% agentethanol 2.5% 2.5% 1.4% 1.5% propanediol 6.6% 6.6% 4.9% 4.0% 15.7% sorbitol 4.0% ethanolamine 1.5% 1.5% 0.8% 0.1% 11.0%  sodium hydroxide3.0% 3.0% 4.9% 1.9% 1.0% sodium cumene sulfonate 2.0% silicone sudssuppressor 0.01%  perfume 0.3% 0.3% 0.7% 0.3% 0.4% 0.6% Compound 16 ofTable 1 0.005%  0.005%  Compound 24 of Table 1 0.005%  Compound 13 ofTable 1 0.008%  Compound 36 of Table 1 0.008%  Compound 21 of Table 10.015%  Liquitint Aqua AS⁴ 0.005%  opacifier⁶ 0.5% water balance balancebalance balance balance balance 100.0%  100.0%  100.0%  100.0%  100.0% 100.0%  ¹diethylenetriaminepentaacetic acid, sodium salt²diethylenetriaminepentakismethylenephosphonic acid, sodium salt³ethylenediaminetetraacetic acid, sodium salt ⁴a non-tinting dye used toadjust formula color ⁵compact formula, packaged as a unitized dose inpolyvinyl alcohol film ⁶Acusol OP 301

Example 2

The following granular detergent formulas are within the scope of thepresent invention.

2a 2b 2c 2d Ingredient wt % wt % wt % wt % Na linear alkylbenzene 3.4%3.3% 11.0% 3.4% sulfonate Na alkylsulfate 4.0% 4.1% 4.0% Na alkylsulfate (branched) 9.4% 9.6% 9.4% alkyl ethoxylate  3.5% type A zeolite37.4%  35.4%  26.8% 37.4%  sodium carbonate 22.3%  22.5%  35.9% 22.3% sodium sulfate 1.0% 18.8% 1.0% sodium silicate  2.2% protease 0.1% 0.2%0.1% sodium polyacrylate 1.0% 1.2%  0.7% 1.0% carboxymethylcellulose 0.1% PEG 600 0.5% PEG 4000 2.2% DTPA 0.7% 0.6% 0.7% fluorescentwhitening agent 0.1% 0.1%  0.1% 0.1% sodium percarbonate 5.0% sodiumnonanoyloxy- 5.3% benzenesulfonate silicone suds suppressor 0.02% 0.02%  0.02%  perfume 0.3% 0.3%  0.2% 0.3% Compound 15 of Table 10.015%¹  Compound 48 of Table 1 0.017%² Compound 38 of Table 1 0.017%³ Compound 33 of Table 1 0.02%⁴  water and miscellaneous balance balancebalance balance ¹formulated as a particle containing 0.5% dye, 99.5% PEG4000 ²formulated as a layered particle containing 2% dye according to US2006 252667 A1 ³formulated as a particle containing 0.5% dye accordingto U.S. Pat. No. 4,990,280 ⁴formulated as a particle containing 0.5% dyewith zeolite

Example 3

The following rinse added fabric conditioning formulas are within thescope of the present invention.

Ingredients 3a 3b 3c 3d Fabric Softening Active^(a) 13.70%  13.70% 13.70%  13.70%  Ethanol 2.14% 2.14% 2.14% 2.14% Cationic Starch^(b)2.17% 2.17% 2.17% 2.17% Perfume 1.45% 1.45% 1.45% 1.45% PhaseStabilizing 0.21% 0.21% 0.21% 0.21% Polymer^(c) Calcium Chloride 0.147% 0.147%  0.147%  0.147%  DTPA^(d) 0.007%  0.007%  0.007%  0.007% Preservative^(e)  5 ppm  5 ppm  5 ppm  5 ppm Antifoam^(f) 0.015% 0.015%  0.015%  0.015%  Compound 45 of Table 1 30 ppm 15 ppm Compound 25of Table 1 30 ppm Compound 30 of Table 1 30 ppm 15 ppm Tinopal CBS-X^(g)0.2  0.2  0.2  0.2  Ethoquad C/25^(h) 0.26 0.26 0.26 0.26 AmmoniumChloride  0.1%  0.1%  0.1%  0.1% Hydrochloric Acid 0.012%  0.012% 0.012%  0.012%  Deionized Water Balance Balance Balance Balance^(a)N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.^(b)Cationic starch based on common maize starch or potato starch,containing 25% to 95% amylose and a degree of substitution of from 0.02to 0.09, and having a viscosity measured as Water Fluidity having avalue from 50 to 84. ^(c)Copolymer of ethylene oxide and terephthalatehaving the formula described in U.S. Pat. No. 5,574,179 at col. 15,lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R¹ isessentially 1,4-phenylene moieties, each R² is essentially ethylene,1,2-propylene moieties, or mixtures thereof.^(d)Diethylenetriaminepentaacetic acid. ^(e)KATHON ® CG available fromRohm and Haas Co. ^(f)Silicone antifoam agent available from Dow CorningCorp. under the trade name DC2310. ^(g)Disodium 4,4′-bis-(2-sulfostyryl)biphenyl, available from Ciba Specialty Chemicals. ^(h)Cocomethylethoxylated [15] ammonium chloride, available from Akzo Nobel

Example 4 Synthesis of mtol-10EO methylthiazolium

Five hundred and forty-nine grams of 85% phosphoric acid, 75 grams of98% sulfuric acid and 9 drops of 2-ethyl hexanol defoamer are added to a100 milliliter three necked flask equipped with a thermometer, coolingbath, and mechanical stirrer. The mixture is cooled and 30.9 grams of2-aminothiazole is added to the flask. The mixture is further cooled tobelow 0° C. after which 105 grams of 40% nitrosyl sulfuric acid areadded while the temperature is maintained below 5° C. After three hoursthe mixture gives a positive nitrite test and 25 grams of sulfamic acidare added slowly while the temperature is kept below 5° C. A negativenitrite test is evident after one hour.

A 2000 milliliter beaker is charged with 190 grams 10 EO m-toluidineintermediate, 200 grams of water, 200 grams of ice and 12 grams of urea.The mixture is cooled to 0° C. The diazo solution is added dropwise tothe beaker over about 30 minutes, while maintaining the temperaturebelow 10° C. The resulting mixture is stirred for several hours andallowed to stand overnight, after which 780 grams of 50% sodiumhydroxide is added to neutralize excess acid to a pH of about 7 whilethe temperature is kept below 20° C. The bottom salt layer is removedand the product is washed with 200 milliliters of a 10% sodium sulfatesolution. The aqueous layer is removed and the desired product isobtained as an orange liquid (240 grams, 70% actives).

One hundred grams of the orange liquid from above and 28.40 grams ofdimethyl sulfate are placed into a 500 milliliter flask equipped with areflux condenser, thermometer, heating mantle and mechanical stirrer.The reaction mixture is heated to 70° C. for two hours. The reaction iscooled and the pH is adjusted to 7 with 10 grams of 20% ammoniumhydroxide and is used without further purification.

Example 5

The procedure of Example 4 is used to make N-ethyl-mtol-5EO

with the difference being the use of the following m-toluidineintermediate:

Example 6

The procedure of Example 5, with the noted changes, is used to make:

Twenty grams of the orange liquid per Example 5, as obtained via Example4, and nine grams of benzyl bromide are placed into a 250 milliliterflask equipped with a reflux condenser, thermometer, heating mantle andmechanical stirrer. The reaction mixture is heated to 70° C. for twohours. The reaction is cooled and the pH is adjusted to 7 with 4 gramsof 50% sodium hydroxide and is used without further purification.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A whitening agent for laundry care compositions comprising a thiazolium dye is selected from (E)-2-((4-((2-hydroxy-3-(2-(2-(2-hydroxyethoxy)ethoxy) ethoxy)propyl)(2-hydroxy-3-(2-(2-hydroxyethoxy)ethoxy)propyl)amino)-2-methylphenyl) diazenyl)-3-methylthiazol-3-ium; (E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy) ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; (E)-2-((4-(bis(14-hydroxy-3,6,9, 12-tetraoxatetradecyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; (E)-2((4-((2(2-(2-acetoxyethoxy)ethoxy)ethyl)(2-(2-acetoxyethoxy) ethyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; (E)-2-((4-(ethyl(14-hydroxy-3,6,9, 12-tetraoxetetradecyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; (E)-2-((4-(benzyl(1, 17-dihydroxy-3,6,9, 12, 15-penteoxaoctedecan-18-yl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; (E)-2-((4-((2-(2-(2-(2,3-dihydroxypropoxy) ethoxy)ethoxy)ethyl)(2-(2-(2,3-dihydroxypropaxy)ethoxy)ethyl)amino)-2-methylphenyl) diazenyl-3-methylthiazol-3-ium; (E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)-3-isopropoxypropyl)(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)-3-isopropoxypropyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; (E)-2-((4-(benzyl(29-hydroxy-3,6,9,12,15,18,21,24,27-nonaoxanonacosyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; (E)-3-ethyl-2-((4-(ethyl(23-hydroxy-3,6,9,12,15,18,21-heptaoxetricosyl)amino)-2-methylphenyl) diazenyl)thiazol-3-ium; (E)-2-((4-((2-(2-hydroxypropoxy)ethyl)(2-(2-(2-hydroxypropoxy) propoxy)ethyl)amino)-2-methylphenyl) diazenyl)-3-methylthiazol-3-ium; (E)-2-((4-(ethyl(23-hydroxy-3,6,9,12,15,18,21-heptaoxatricosyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; (E)-3-ethyl-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)ethyl)(2-(2-hydroxyethoxy)ethyl)amino)-2-methylphenyl)diazenyl)thiazol-3-ium; (E)-3-ethyl-2-((4-((2-(2-hydroxypropoxy)ethyl)(2-(2-(2-hydroxypropoxy)propoxy)ethyl)amino)-2-methylphenyl) diazenyl)thiazol-3-ium; (E)-2-((4-((2-(2-(2-hydroxyethoxy)ethoxy)propyl)2-(2-hydroxyethoxy)propyl)amino)-2-methylphenyl)diazenyl)-3-methylthiazol-3-ium; and mixtures thereof. 